EP3470386A1 - Procédé de traitement de la biomasse de déchets agricoles lignocellulosiques et/ou de déchets contenant des groupes fonctionnels phénoliques - Google Patents

Procédé de traitement de la biomasse de déchets agricoles lignocellulosiques et/ou de déchets contenant des groupes fonctionnels phénoliques Download PDF

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Publication number
EP3470386A1
EP3470386A1 EP17382674.4A EP17382674A EP3470386A1 EP 3470386 A1 EP3470386 A1 EP 3470386A1 EP 17382674 A EP17382674 A EP 17382674A EP 3470386 A1 EP3470386 A1 EP 3470386A1
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EP
European Patent Office
Prior art keywords
reactor
biomass
outlet valve
temperature
fraction
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EP17382674.4A
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German (de)
English (en)
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EP3470386B1 (fr
Inventor
Santiago Alier Uriach
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Energies Termiques Basiques Sl
Energies Termiques Basiques Sl
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Energies Termiques Basiques Sl
Energies Termiques Basiques Sl
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Priority to ES17382674T priority Critical patent/ES2785648T3/es
Priority to EP17382674.4A priority patent/EP3470386B1/fr
Publication of EP3470386A1 publication Critical patent/EP3470386A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L9/00—Treating solid fuels to improve their combustion
    • C10L9/08—Treating solid fuels to improve their combustion by heat treatments, e.g. calcining
    • C10L9/083—Torrefaction
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
    • C05F5/00—Fertilisers from distillery wastes, molasses, vinasses, sugar plant or similar wastes or residues, e.g. from waste originating from industrial processing of raw material of agricultural origin or derived products thereof
    • C05F5/002—Solid waste from mechanical processing of material, e.g. seed coats, olive pits, almond shells, fruit residue, rice hulls
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L5/00—Solid fuels
    • C10L5/40—Solid fuels essentially based on materials of non-mineral origin
    • C10L5/44—Solid fuels essentially based on materials of non-mineral origin on vegetable substances
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
    • Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
    • Y02A40/20—Fertilizers of biological origin, e.g. guano or fertilizers made from animal corpses
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock
    • Y02P20/145—Feedstock the feedstock being materials of biological origin

Definitions

  • the present invention relates to the field of methods for treating the biomass of lignocellulosic agricultural waste and/or agricultural waste containing phenolic functional groups, and is intended for obtaining a product for soil improvement, such as acidity regulators, fertilizers, etc., a biofuel, phenolic products and other by-products.
  • the treatment of the biomass of the invention includes adding a catalyst to the biomass, where said catalyst mixes with the biomass, and then proceeding with a first drying step in a first reactor for evaporating the water contained in the biomass, and then with a torrefaction step in a second reactor for torrefying the biomass to be treated under anoxic conditions, all for obtaining more valuable products, particularly biofuels and phenolic products, which are extracted in the form of gases that are subsequently liquefied and fractionated.
  • thermochemical treatment of biomass under anoxic conditions causing torrefaction, pyrolysis or gasification of said biomass is known, with the existence of different plants designed for such purpose.
  • patent document EP3048161 belonging to the same applicant as the present invention discloses a plant provided with a first reactor and a second reactor that are connected in series to carry out thermal treatment of a biomass introduced into said plant, obtaining a gas fraction that can be condensed.
  • said patent document does not describe a method which allows obtaining biofuels, fertilizers and/or products for soil improvement from the biomass of a wide range of lignocellulosic agricultural waste and/or agricultural waste containing phenolic functional groups by means of adding catalysts and a torrefaction-specific process.
  • said patent document does not at any time mention the use of catalysts in a thermal reaction within temperature ranges that are the determining factors of a torrefaction reaction.
  • the present invention relates to a method for treating the biomass of lignocellulosic agricultural waste and/or waste containing phenolic functional groups for obtaining a biofuel.
  • Said method leads to valorization (an increase in value) of the biomass, converting a given product into a different product or products that are more valuable than the original product, such as biofuels.
  • Said biomass is treated at least in a first elongated thermochemical reaction reactor and a second elongated thermochemical reaction reactor that are connected in line, such that the biomass goes through the first reactor and then the second reactor.
  • each of the first and second reactors is provided with:
  • Plants of this type which are provided with two reactors that are connected in line and house a screw conveyor allow performing two different treatments with different conditions, thereby obtaining a different gas fraction in each of the reactors.
  • the inlet and outlet valves which prevent the free entry of air allow creating near-anoxic or anoxic conditions (with the absence or a low content of oxygen in the inner atmosphere of the reactor). This allows preventing oxidation processes and other chemical reactions which would hinder biofuel production.
  • thermochemical reaction chamber and/or in said thermochemical reaction chamber, for example on the actual shaft of the screw conveyor.
  • An embodiment which combines both heaters would allow quick and uniform heating of the reactor content.
  • the method proposes the following novel steps:
  • a drying step is therefore performed in the first reactor, consisting of increasing the temperature of the biomass mixture, which can be introduced into the first reactor at an ambient temperature between 10°C and 25°C, for example, until reaching a temperature comprised between 120°C and 190°C, or more preferably between 160°C and 190°C. Said drying step will be extended for a period of between 2 and 3 minutes, enough to cause most of the moisture contained in the biomass mixture to evaporate, but not enough to degrade or fractionate the compounds required for obtaining biofuel and other phenolic products which will remain in the dry biomass.
  • the evaporated water will be extracted from the first reactor in the form of a gas fraction through the gas outlet valve.
  • drying step will last for the time it takes for the biomass to be conveyed from the inlet valve to the solid outlet valve by means of the adjustable-speed screw conveyor.
  • the biomass introduced into the first reactor will be mixed with a catalyst which will comprise at least a mixture of calcium and magnesium carbonates.
  • Said catalyst will preferably be mixed with the biomass before being introduced into the first reactor, although the catalyst can be supplied to the first reactor separately from the biomass, where the mixing takes place inside the first reactor. The catalyst will therefore reach the second reactor preheated, preventing rises in temperature.
  • the biomass introduced into the first reactor will have a water content equal to or less than 20%, which allows obtaining a completely dry biomass with negligible water content upon the end of the treatment thereof in the first reactor.
  • biomass with a water content greater than 25% would prevent obtaining dry biomass after passage through the first reactor for the time period the drying step is stipulated to last, which can result in lower treatment process yields, particularly increasing the gas fraction in the second reactor which will also increase the aqueous condensate fraction.
  • the dry biomass obtained in the first reactor will be extracted therefrom through the solid outlet valve of the first reactor, and introduced into the second reactor through the inlet valve of the second reactor, preventing or minimizing the entry of atmospheric air into said second reactor. It is understood that the solid outlet valve of the first reactor and the inlet valve of the second reactor can be one and the same valve that is shared by both reactors and performs both functions.
  • an inert gas for example and preferably, CO 2 and/or N 2 , is injected into the second reactor. Said inert gas prevents the outside air from entering the second reactor, and expels any remaining air containing O 2 from the interior of the second reactor.
  • a torrefaction step consisting of increasing the temperature of the biomass mixture until reaching a temperature comprised between 200°C and 300°C for a period between 3 and 3.5 minutes, enough to cause torrefaction of the dry biomass, causing a chemical reaction between the catalyst and the lignocellulosic materials and/or phenolic functional groups of the dry biomass, thereby generating the desired, high added value products, including biofuels.
  • torrefaction step will last for the time it takes for the dry biomass to be conveyed from the inlet valve to the solid outlet valve by means of the screw conveyor.
  • CO 2 as an inert gas can favor this reaction by also collaborating in the chemical reaction that has been described.
  • the torrefaction step will generate a gas fraction which will contain the desired, high added value compounds, and a solid fertilizer fraction or a product for soil improvement.
  • the gas fraction will be extracted from the second reactor through the gas outlet valve of the second reactor. Said gas fraction will then be introduced into a condenser where a liquid fraction at room temperature will be separated from a gas fraction at room temperature.
  • the obtained liquid fraction will contain an organic liquid phase comprising C14-C18 biofuel and phenols, and an aqueous liquid phase comprising sugars and acids comprising acetic acid.
  • the organic liquid and aqueous liquid phases can then be separated by density, with one phase floating on top of the other phase in strata.
  • the catalyst will be metered for obtaining a biomass mixture with a pH comprised between 8.5 and 9.5.
  • a pH comprised between 8.5 and 9.5.
  • the described method is proposed for the described method to be performed continuously, where the biomass is introduced into the first reactor at a controlled speed, and where the screw conveyors of the first reactor and the second reactor are adjusted so that the biomass remains inside the first reactor and inside the second reactor for the times mentioned above, and so that the indicated temperature gradients are generated.
  • the catalyst in some cases, and particularly for all pruning of biomass originating from agricultural waste such as grapevines, olive trees, apple trees, tomatoes and others, it is contemplated for the catalyst to also include lanthanide and/or cerium earth oxides. This can be particularly beneficial according to the type of biomass introduced into the system.
  • the catalyst will be mixed with the biomass in the form of dry powder, which increases the contact surface thereof and speeds up the reaction.
  • the biomass used will be selected from peels, i.e., waste from pressing plant material, grape peels, apple peels, tomato peels, olive meal, i.e., waste generated from the pressing of olives, where it can also be applied to a large number of lignocellulosic agricultural waste and/or waste containing phenolic functional groups, such as waste from pruning olive trees, grapevines, apple trees, or tomato plants.
  • peels i.e., waste from pressing plant material, grape peels, apple peels, tomato peels
  • olive meal i.e., waste generated from the pressing of olives
  • the torrefied solid fraction extracted from the second reactor is introduced into a third cooling reactor which has features similar to the first and second reactors, but lacking both thermal insulation and heaters, and is connected to a cooler, for example, through cooling fluid ducts. It is contemplated for said cooling device to be a heat recovery device which recovers heat from the biomass and uses it for other purposes within the same plant.
  • the proposed method for treating the biomass of lignocellulosic agricultural waste and/or waste containing phenolic functional groups is applied by means of an industrial plant for thermochemical treatment of biomass under near-anoxic or anoxic conditions that is described below in an illustrative and non-limiting manner and shown in a schematic manner in Figure 1 .
  • the purpose of the proposed method is to convert the biomass into a different product or different products, obtaining solid, liquid and/or gas fractions that are of commercial interest and have greater economic value than that of the biomass used for obtaining same.
  • the biomass of lignocellulosic agricultural waste and/or waste containing phenolic functional groups used will be waste generated from the pressing of, preferably, olives or grapes, although waste generated from the pressing of other plants, or even waste generated from the pruning of these plants, are contemplated.
  • the proposed industrial valorization plant includes a first reactor implementing a biomass drying step, a second reactor implementing a biomass torrefaction step, and a third reactor implementing a cooling step for cooling the remaining solid fraction after the first two steps have been completed.
  • each of the first, second and third reactors comprise the following components:
  • the heaters will consist of electric heaters that are either resistances or infrared-emitting electric heaters.
  • a system for condensing the gas fraction by cooling, optionally including cyclonic filtration of the solid particles of the gas fraction, and a system for separating liquid fractions by density, will complete the plant.
  • two cyclonic centrifuges are arranged in series, and it is contemplated for said cyclonic centrifuges to be thermally insulated or to even be heated to prevent condensation of the torrefied gas fraction therein.
  • the solid particles obtained from this process can be disposed of or mixed with the torrefied solid fraction.
  • the proposed method consists of mixing the biomass of lignocellulosic agricultural waste and/or waste containing phenolic functional groups, said biomass having a water content preferably equal to or less than 20% and having been ground until obtaining a granular composition with fragments having a mean size between 1 and 10 mm, preferably between 2 to 6 mm, with a catalyst comprising at least a mixture of calcium and magnesium carbonates in the form of powder, at a ratio of 10 to 1 by weight with respect to the biomass with which it mixes.
  • the biomass resulting from said mixing is introduced into the first reactor through the inlet valve thereof at room temperature for performing a drying step.
  • the screw conveyor inside said first reactor will be adjusted to move the biomass along the entire length of the first reactor in a time between 2 and 3 minutes. Therefore, the speed of introducing the biomass through the inlet valve and the operating speed of the screw conveyor will be coordinated, for example, by means of a controller device, such as a programmable logic controller.
  • the heaters of the first reactor will increase the temperature of the biomass to a temperature close to 190°C, without ever reaching 200°C, for the time that said biomass remains inside the first reactor, causing the evaporation of the water contained in the biomass, which will form vapor.
  • the vapor will be discharged through the gas outlet valve of the first reactor and released into the atmosphere.
  • the dry biomass resulting from the drying step is then extracted from the first reactor through the solid outlet valve, pushed by the screw conveyor, and immediately introduced into the second reactor through the inlet valve thereof, preventing the entry of outside air into the second reactor.
  • An inert gas in this case CO 2 , is also injected into the second reactor to displace the rest of the O 2 that may remain inside the second reactor, thereby assuring anoxic conditions.
  • the heaters inside the second reactor will increase the temperature of the biomass above 200°C, being able to reach 300°C, depending on the type of biomass introduced, causing torrefaction of the dry biomass and stimulating the chemical reaction with the included catalyst, releasing gases and vapors. In no case will the mentioned 300°C be exceeded, because in such case a pyrolysis reaction that would destroy some of the compounds to be obtained would start.
  • the screw conveyor of the second reactor will be configured for conveying the dry biomass along the entire length of the second reactor in about 3 minutes, during which time said torrefaction step will take place.
  • the torrefied gas fraction resulting from said torrefaction, including said released vapors and gases, will be extracted from the second reactor 2 through its gas outlet valve 41, and cooled in a condensation tower 81 after filtering out the solid particles in a cyclonic filter 80, obtaining at least an organic liquid phase comprising C14-C18 biofuel and phenols, and an aqueous liquid phase comprising sugars and acids comprising acetic acid, said liquid phases being able to be separated by density.
  • the torrefied solid waste contained in the second reactor 2 has properties as a soil improver and/or fertilizer (requiring the addition of a complementary substance in some cases), for example a soil improver for regulating acidity, and can be extracted from the second reactor 2 through the solid outlet valve 42 so that it can be extracted from the plant for use after going through a third reactor 3 where a cooling step is applied.
  • a soil improver and/or fertilizer requiring the addition of a complementary substance in some cases
  • a soil improver for regulating acidity for example a soil improver for regulating acidity
  • the condensation tower 81 can be cooled by means of a cooling fluid in a cooler 90 integrated in the plant. Said cooler can also be responsible for cooling the mentioned third reactor 3, achieving rapid cooling of the torrefied solid fraction contained therein.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Mechanical Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Botany (AREA)
  • Environmental & Geological Engineering (AREA)
  • Processing Of Solid Wastes (AREA)
EP17382674.4A 2017-10-11 2017-10-11 Procédé de traitement de la biomasse de déchets agricoles lignocellulosiques et/ou de déchets contenant des groupes fonctionnels phénoliques Active EP3470386B1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
ES17382674T ES2785648T3 (es) 2017-10-11 2017-10-11 Método para tratamiento de biomasa de residuos agrícolas lignocelulósicos y/o residuos que contienen grupos funcionales fenólicos
EP17382674.4A EP3470386B1 (fr) 2017-10-11 2017-10-11 Procédé de traitement de la biomasse de déchets agricoles lignocellulosiques et/ou de déchets contenant des groupes fonctionnels phénoliques

Applications Claiming Priority (1)

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EP17382674.4A EP3470386B1 (fr) 2017-10-11 2017-10-11 Procédé de traitement de la biomasse de déchets agricoles lignocellulosiques et/ou de déchets contenant des groupes fonctionnels phénoliques

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EP3470386A1 true EP3470386A1 (fr) 2019-04-17
EP3470386B1 EP3470386B1 (fr) 2020-01-08

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022253366A1 (fr) * 2022-03-28 2022-12-08 Vysoká Škola Báňská - Technická Univerzita Ostrava Procédé d'enrichissement d'un gaz produit par torréfaction et pyrolyse de biomasse avec du méthane et appareil pour la mise en œuvre du procédé

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2321341T3 (es) 2005-07-20 2009-06-04 Panzani Procedimiento para el tratamiento de granos de cereales enteros descortezados y dispositivo para la realizacion de dicho procedimineto.
US20120111714A1 (en) * 2009-07-01 2012-05-10 Circa Group Pty Ltd Method for converting lignocellulosic materials into useful chemicals
US20130326935A1 (en) * 2012-06-11 2013-12-12 Bepex International, Llc System for treating biomass
US20140013657A1 (en) 2011-03-23 2014-01-16 Centre De Recherche Industrielle Du Québec (Criq) System and process for thermochemical treatment of matter containing organic compounds
US20150321980A1 (en) * 2014-05-08 2015-11-12 Exxonmobil Research And Engineering Company Stabilization of pyrolysis bio-oil using in-situ hydrogenation
EP3048161A1 (fr) 2015-01-20 2016-07-27 Energies Tèrmiques Bàsiques, SL Installation industrielle de traitement thermochimique de biomasse
WO2016170439A1 (fr) * 2015-04-22 2016-10-27 North-West University Production d'une matière de charge d'alimentation carbonée à partir d'une source de carbone issue de déchets

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2321341T3 (es) 2005-07-20 2009-06-04 Panzani Procedimiento para el tratamiento de granos de cereales enteros descortezados y dispositivo para la realizacion de dicho procedimineto.
US20120111714A1 (en) * 2009-07-01 2012-05-10 Circa Group Pty Ltd Method for converting lignocellulosic materials into useful chemicals
US20140013657A1 (en) 2011-03-23 2014-01-16 Centre De Recherche Industrielle Du Québec (Criq) System and process for thermochemical treatment of matter containing organic compounds
US20130326935A1 (en) * 2012-06-11 2013-12-12 Bepex International, Llc System for treating biomass
US20150321980A1 (en) * 2014-05-08 2015-11-12 Exxonmobil Research And Engineering Company Stabilization of pyrolysis bio-oil using in-situ hydrogenation
EP3048161A1 (fr) 2015-01-20 2016-07-27 Energies Tèrmiques Bàsiques, SL Installation industrielle de traitement thermochimique de biomasse
WO2016170439A1 (fr) * 2015-04-22 2016-10-27 North-West University Production d'une matière de charge d'alimentation carbonée à partir d'une source de carbone issue de déchets

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022253366A1 (fr) * 2022-03-28 2022-12-08 Vysoká Škola Báňská - Technická Univerzita Ostrava Procédé d'enrichissement d'un gaz produit par torréfaction et pyrolyse de biomasse avec du méthane et appareil pour la mise en œuvre du procédé
CZ310023B6 (cs) * 2022-03-28 2024-05-15 Vysoká Škola Báňská - Technická Univerzita Ostrava Způsob obohacení plynu vzniklého torefakcí a pyrolýzou biomasy methanem a zařízení k provádění tohoto způsobu

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EP3470386B1 (fr) 2020-01-08
ES2785648T3 (es) 2020-10-07

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